TECHNICAL FIELD
[0001] The present invention relates to cleaning and soil suspending compositions which
employ alkoxylated, especially ethoxylated and/or propoxylated, polyalkyleneamine
polymers to boost soil dispersing performance. Fabric laundering, dishwashing and
hard-surface cleaning compositions with improved soil dispersing properties are provided.
BACKGROUND OF THE INVENTION
[0002] Detergent formulators are faced with the task of devising products to remove a broad
spectrum of soils and stains from fabrics. Chemically and physicochemically, the varieties
of soils and stains ranges the spectrum from polar soils, such as proteinaceous, clay,
and inorganic soils, to non-polar soils, such as soot, carbon-black, byproducts of
incomplete hydrocarbon combustion, and organic soils. Detergent compositions have
become more complex as formulators attempt to provide products which handle all types
concurrently.
[0003] Formulators have been highly successful in developing traditional dispersants which
are particularly useful in suspending polar, highly charged, hydrophilic particles
such as clay. As yet, however, dispersants designed to disperse and suspend non-polar,
hydrophobic-type soils and particulates have been more difficult to develop. Without
wishing to be limited by theory, it is believed that the first step for dispersion
formation is the adsorbance of the soil dispersing agent onto the soil of interest.
For clay-like soils, the soil dispersing agent must adsorb onto either a negatively
charged surface or positively charged edge. For organic particulates, the soil dispersing
agent must adsorb onto a hydrophobic surface with little or no charge. Hence, for
polar soils, like clay, a dispersing agent with some charge, such as charged, highly
ethoxylated polyamines, are employed. However, these charged dispersing agents have
no driving force for adsorbing onto organic, non-polar particulates.
[0004] It has now been discovered that compositions comprising substantially noncharged,
alkoxylated, especially ethoxylated/propoxylated, polyalkyleneamine polymers can be
used to provide effective, improved soil dispersing (especially on non-polar soils)
in wash liquors. Further, said ethoxylated/propoxylated polyalkyleneamine polymers
appear to whiten/clean fabrics and boost the cleaning performance of hard-surface
and dishware detergent compositions.
[0005] Accordingly, it is an object of the present invention to provide improved cleaning
and soil dispersing compositions using substantially noncharged, ethoxylated/propoxylated
polyalkyleneamine polymers. It is another object herein to provide a means for dispersing
soils and providing whitening/cleaning benefits to fabrics and dishware using the
soil dispersing systems of this invention. These and other objects are secured herein,
as will be seen from the following disclosures.
BACKGROUND ART
[0006] The use of ethoxylated amines is reported in the following United States Patents:
4,891,160; 4,676,921; and 4,597,898. Additional uses of polyalkyleneamines polymers
are reported in the following United States Patents: 5,183,601; 4,654,043; 4,645,611;
4,634,544; and 4,171,278. Also see European Patent Application 206,513 Al and 042,187
Al.
SUMMARY OF THE INVENTION
[0007] The present invention encompasses soil dispersing compositions comprising substantially
noncharged alkoxylated, preferably ethoxylated and or propoxylated, polyalkyleneamine
polymers.
[0008] When used herein the term "ethoxylate/propoxylate" means those alkoxylate units which
are within the scope of this invention as defined hereinafter. The ethoxylated/ propoxylated
polyalkyleneamine polymers are used in an effective amount in the compositions and
processes herein. By "effective amount" is meant an amount which is sufficient, under
whatever comparative test conditions are employed, to enhance the dispersion of soils
in wash liquors and to provide whitening and/or cleaning to the target substrate.
Thus, in a fabric laundering operation, the target substrate will typically be a fabric
stained with, for example, various food stains. For automatic dishwashing, the target
substrate may be, for example, a porcelain cup or plate with tea stain or a polyethylene
plate stained with beef gravy. The test conditions will vary, depending on the type
of washing appliance used and the habits of the user. Thus, front-loading laundry
washing machines of the type employed in Europe generally use less water and higher
detergent concentrations than do top-loading U.S.-style machines. Some machines have
considerably longer wash cycles than others. Some users elect to use very hot water;
others use warm or even cold water in fabric laundering operations. Of course, the
performance of the soil dispersing agent will be affected by such considerations,
and the levels used in fully-formulated detergent and soil dispersing compositions
can be appropriately adjusted.
[0009] Preferably, the soil dispersing compositions comprise at least 0.1%, preferably from
0.1% to 15%, more preferably from 0.5%, to 10%, by weight of composition, of ethoxylated/propoxylated
polyalkyleneamine polymers. The polyalkyleneamines comprise a nitrogen-containing
backbone with an average molecular weight of from 600 to 10,000, preferably from 1,000
to 3,000. Said polymers have an average alkoxylation of from 5 to 10, preferably from
0.7 to 8, most preferably from 0.7 to 4, per nitrogen, provided that when the composition
is a liquid laundry composition, the amount of polyalkylene amine polymer is not 20
ppm in 2000 ppm of the composition and the polyalkylene amine polymer is not a polymer
of an average molecular weight of 600 having an average ethoxylation of 3 or a polymer
of average molecular weight of 1800 having an average ethoxylation of 5. Further said
alkoxylated polyalkyleneamine polymers may comprise up to 4, but preferably 1 or less,
propoxylates or longer alkoxylate units per available site on the nitrogens. By "per
available site on the nitrogens" is meant that each H of the NH moiety can be substituted
with up to 4 propoxylates or longer alkoxylate units. Thus, after alkoxylation of
a NH
2 site, there can then be up to 8 propoxylates or long alkoxylate units connected to
the nitrogen. Preferably, the propoxylate or longer alkoxylate units in the alkoxylate
systems are added to the polyalkylene-amine first, before the ethoxylate units.
[0010] The invention further encompasses compositions comprising from 1% to 55% of a detersive
surfactant and ethoxylated/propoxylated polyalkyleneamine polymers.
[0011] Additionally, the invention encompasses detergent compositions, including laundry
detergents, detergent bars, automatic dishwashing detergents, and hard-surface cleaners,
comprising conventional surfactants and other detersive ingredients.
[0012] The invention also encompasses a method for improving the soil dispersing performance
of detergent compositions, comprising adding thereto an effective amount of an ethoxylated/propoxylated
polyalkyleneamine polymer. This provides a method for whitening and/or cleaning fabrics,
hard-surfaces, or dishware comprising contacting said fabrics, hart-surfaces, or dishware
with an aqueous medium comprising said compositions. Again, without wishing to be
limited by theory, it is believed that the whitening/cleaning benefits are obtained
by the suspension of the soil and particulate material in the wash liquor, thus preventing
its redeposition onto the fabric or other surfaces in the wash liquor. These benefits
appear after repeated soiling/washing cycles. The number of cycles necessary for the
benefit to become visible is dependent on the level of soil dispersing agent used
in the wash cycle, the level of soiling present in the wash liquor, and the overall
efficiency of the base detergent to which the soil dispersing agent is added.
[0013] As a practical matter, and not by way of limitation, the compositions and processes
herein can be adjusted to provide on the order of at least one part per ten million
of the active ethoxylated/propoxylated polyalkyleneamine polymer species in the aqueous
washing medium, and will preferably provide from 0.1 ppm to 700 ppm, more preferably
from 0.5 ppm to 500 ppm, most preferably from 1 ppm to 100 ppm, of the ethoxylated/propoxylated
polyalkyleneamine polymer species in the washing medium.
[0014] All percentages, ratios and proponions herein are by weight, unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
[0015] In contrast to the charged polymers in the art, the ethoxylated/propoxylated polyalkyleneamine
polymers of this invention are substantially noncharged, low molecular weight, water
soluble, and lightly alkoxylated, preferably ethoxylated/propoxylated. By "lightly"
is meant the polymers of this invention average from 0.5 to 10 alkoxylations per nitrogen.
By "substantially noncharged" is meant that there is no more than 2 positive charges
for every 40 nitrogens present in the backbone of the polyalkyleneamine polymer.
[0016] The preferred ethoxylated/propoxylated polyalkyleneamines of this invention are of
the formula:
wherein each R
1 is independently C
2-C
12 alkylene, alkenylene, arylene or alkarylene; each R
2 is independently H, a straight, branched, or cyclic C
1-C
8 alkyl moiety, phenyl, benzyl, a C
1-C
8 aroyl or alkanoyl moiety, especially benzoyl, or the moiety -L-X; wherein X is a
nonionic group, especially H, or an anionic group, such as sulfate, and L is a hydrophilic
chain which contains the polyoxyalkylene moiety [(R
5O)
m'(CH
2CH
2O)
n'-(R
5O)
m"(CH
2CH
2O)
n"], wherein each R
5 is independently H, C
3-C
4 alkylene or hydroxyalkylene, m'+m"= m, n'+n"= n, wherein m is from 0 to 4, n is from
0 to 16, preferably from 0 to 10, m+n is from 1 to 16, preferably from 1 to 10, and
provided that at least 0.5 of the R
2 moieties per nitrogen is -L-X; w is 1 or 0, provided that when w = 0, each terminal
R
1 is independently C
2-C
12 alkyl, alkanyl aryl or alkenyl x+y+z is at least 14; and B represents a continuation
of this structure by branching. Said polymer has an average alkoxylation of from about
0.5 to about 10 per nitrogen, provided that when the composition is a liquid laundry
composition, the amount of polyalkylene amine polymer is not 20 ppm in 2000 ppm of
the composition and the polyalkylene amine polymer is not a polymer of an average
molecular weight of 600 having an average ethoxylation of 3 or a polymer of average
molecular weight of 1800 having an average ethoxylation of 5.
[0017] Although branched backbones are preferred, linear and cyclic polymer backbones are
possible. The relative proportions of primary, secondary and tertiary amine groups
present in the polymer prior to alkoxylation can vary, depending on the manner of
preparation. The distribution of amine groups is typically as follows:
--CH
2CH
2-NH
2 25%
--CH
2CH
2-NH-- 50%
--CH
2CH
2-N-- 25%.
[0018] In the preceding formula, R
1 can be branched or linear (e.g. --CH
2CH
2--, --CH
2--CH
2--CH
2--, --CH
2-C(C
6H
5)H-- , alkylene, alkenylene, alkarylene R
1 is preferably C
2-C
6 alkylene. However, for the ethoxylated polyalkyleneamines and polyalkyleneimines,
especially at higher molecular weights, C
2-C
3 alkylenes (ethylene, propylene) are preferred for R
1 with ethylene being most preferred.
[0019] At least 0.5 of the R
2 moieties per nitrogen is preferably the moiety -L-X. In the preceding formula, hydrophilic
chain L usually consists entirely of the polyoxyalkylene moiety [(R
5O)
m'(CH
2CH
2O)
n'-(R
5O)
m"(CH
2CH
2O)
n"]. The moieties --(R
5O)
m' or
m"--and --(CH
2CH
2O)
n' or
n"-- of the polyoxyalkylene moiety can be mixed together (e.g., random ordered) or
preferably form blocks of -- (R
5O)
m' or
m"- and -(CH
2CH
2O)
n, or
n"- moieties. R
5 is preferably C
3H
6 (propylene). For this invention, m is preferably from 0 to 4, most preferably 0,
i.e., the polyoxyalkylene moiety consists entirely of the moiety --(CH
2CH
2O)
n' or
n"--. The moiety -(CH
2CH
2O)
n, or
n"-- preferably comprises on average at least 85% by weight of the polyoxyalkylene moiety
and most preferably 100% by weight (i.e., when m is 0).
[0020] In the preceding formula, X can be any compatible anionic group, especially sulfate,
or nonionic group. Suitable nonionic groups include C
1-C
4 alkyl or hydroxyalkyl ester or ether groups, preferably the acetate ester or methyl
ether, respectively; hydrogen (H); or mixtures thereof. The particularly preferred
nonionic group is H.
[0021] Particularly preferred ethoxylated/propoxylated polyalkylamine polymers are the ethoxylated
C
2-C
3 polyakyleneamines and polyalkyleneimines, such as the ethoxylated polyethyleneamines
(PEAs) and polyethyleneimines (PEIs).
[0022] In the polyalkyleneimines and polyalkyleneamines, each hydrogen atom attached to
each nitrogen atom represents an active site for subsequent ethoxylation. These PEAS
can be obtained by reactions involving ammonia and ethylene dichloride. See U.S. Pat.
No. 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of
PEAs.
[0023] The PEIs used in preparing the compounds of the present invention have a molecular
weight of at least 600 prior to ethoxylation, which represents at least 14 units.
[0024] These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence
of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide,
hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are disclosed
in U.S. Pat. No. 2k182,306 to Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No. 3,033,746
to Mayle et al., issued May 8, 1962; U.S. Pat. No. 2,208, 095 to Esselmann et al.,
issued July 16, 1940; U.S. Pat. No. 2,806,839 to Crowther, issued Sept. 17, 1957;
and U.S. Pat. No. 2,533,696 to Wilson, issued May 21, 1951.
[0025] Methods for Making Ethoxylated Amines - The ethoxylated compounds of the present invention can be prepared by standard
methods for ethoxylating amines. For the polyamines such as the polyalkyleneamines
and polyalkyleneimines, there is preferably an initial step of condensing sufficient
ethylene oxide to provide 2-hydroxyethyl groups at each reactive site (hydroxyethylation).
The appropriate amount of ethylene oxide is then condensed with these 2-hydroxyethylamines
using an alkali metal (e.g., sodium or potassium) hydride or hydroxide as the catalyst
to provide the respective ethoxylated amines. If desired, the alkali metal catalyst
can be added when the hydroxyethylation step is incomplete. This results in a less
uniform distribution of ethoxylation across the reactive sites than when the catalyst
is added after hydroxyethylation is complete. The total degree of ethoxylation per
reactive site (NH) can be determined according to the following formula:
wherein E is the total number of moles of ethylene oxide condensed (including hydroxyethylation),
A is the number of moles of the starting amine, and R is the number of reactive sites
for the starting amine.
[0026] As indicated hereinbefore, the alkoxylated polyalkyleneamines of this invention are
substantially noncharged, although it is recognized that a limited number of positively
charged sites may be present in the polymers. Thus, this invention includes those
polymers which have up to 2 charged sites per 40 nitrogen sites. The charged sites
may be formed by quaternization or by hydrogen protonation. It is believed, however,
that the preferred pH ranges of this invention ensures that the soil dispersing agents
of this invention remain essentially uncharged in the washing solution. When the soil
dispersing agents of this invention are used, optimum performance is obtained with
washing solutions wherein the pH of such solution is above 9, preferably between 9.5
and 12. Such pH can be obtained with substances commonly known as buffering agents,
which are optional components of the bleaching systems herein.
Adjunct Ingredients
[0027] The compositions herein can optionally include one or more other detergent adjunct
materials or other materials for assisting or enhancing cleaning performance, treatment
of the substate to be cleaned, ot to modify the aesthetics of the detergent composition
(e.g., perfumes, colorants and dyes). The following are illustrative examples of such
adjunct materials.
[0028] Detersive Surfactants - Nonlimiting examples of surfactants useful herein typically at levels from 1% to
55%, by weight, include the conventional C
11-C
18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C
10-C
20 alkyl sulfates ("AS"), the C
10-C
18 secondary (2,3) alkyl sulfates of the formula CH
3(CH
2)
x(CHOSO
3-M
+) CH
3 and CH
3 (CH
2)
y(CHOSO
3-M
+) CH
2CH
3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate,
the C
10-C
18 alkyl alkoxy sulfates ("AE
xS"; especially EO 1-7 ethoxy sulfates), C
10-C
18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C
10-18 glycerol ethers, the C
10-C
18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C
12-C
18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C
12-C
18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates
and C
6-C
12 alkyl phenol alkoxytates (especially ethoxylates and mixed ethoxy/propoxy), C
12-C
18 betaines and sulfobetaines ("sultaines"), C
10-C
18 amine oxides can also be included in the overall compositions. The C
10-C
18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include
the C
12-C
18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the
N-alkoxy polyhydroxy fatty acid amides, such as C
10-C
18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C
12-C
18 glucamides can be used for low sudsing. C
10-C
20 conventional soaps may also be used. If high sudsing is desired, the branched-chain
C
10-C
16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts.
[0029] Builders - Detergent builders can optionally be included in the compositions herein to assist
in controlling mineral hardness. Inorganic as well as organic builders can be used.
Builders are typically used in fabric laundering compositions to assist in the removal
of particulate soils.
[0030] The level of builder can vary widely depending upon the end use of the composition
and its desired physical form. When present, the compositions will typically comprise
at least 1% builder. Liquid formulations typically comprise from 5% to 50%, more typically
5% to 30%, by weight, of detergent builder. Granular formulations typically comprise
from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder.
Lower or higher levels of builder, however, are not meant to be excluded.
[0031] Inorganic or P-containing detergent builders include, but are not limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates,
phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders are required in some
locales. Importantly, the compositions herein function surprisingly well even in the
presence of the so-called "weak" builders (as compared with phosphates) such as citrate,
or in the so-called "underbuilt" situation that may occur with zeolite or layered
silicate builders.
[0032] Examples of silicate builders are the alkali metal silicates, particularly those
having a SiO
2:Na
2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium
silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly
abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder
does not contain aluminium. NaSKS-6 has the delta-Na
2SiO
5 morphology form of layered silicate. It can be prepared by methods such as those
described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred
layered silicate for use herein, but other such layered silicates, such as those having
the general formula NaMSi
xO
2x+1·yH
2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and
y is a number from 0 to 20, preferably 0 can be used herein. Various other layered
silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and
gamma forms. As noted above, the delta-Na
2SiO
5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful
such as for example magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds
control systems.
[0033] Examples of carbonate builders are the alkaline earth and alkali metal carbonates
as disclosed in German Patent Application No. 2.321.001 published on November 15,
1973.
[0034] Aluminosilicate builders are useful in the present invention. Aluminosilicate builders
are of great importance in most currently marketed heavy duty granular detergent compositions,
and can also be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
M
z(zAlO
2)
y]·xH
2O
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range
from 1.0 to 0.5, and x is an integer from 15 to 264.
[0035] Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates
can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates
or synthetically derived. A method for producing aluminosilicate ion exchange materials
is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred
synthetic crystalline aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially preferred embodiment, the crystalline aluminosilicate ion exchange material
has the formula:
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated
zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has
a particle size of 0. 1-10 microns in diameter.
[0036] Organic detergent builders suitable for the purposes of the present invention include,
but are not restricted to, a wide variety of polycarboxylate compounds. As used herein,
"polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably
at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition
in acid form, but can also be added in the form of a neutralized salt. When utilized
in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium
salts are preferred.
[0037] Included among the polycarboxylate builders are a variety of categories of useful
materials. One important category of polycarboxylate builders encompasses the ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S Patent 3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18,
1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al,
on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly
alicyclic compounds, such as those described in U.S Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
[0038] Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers
of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal,
ammonium and substituted ammonium salts of polyacetic acids such as ethylmediamine
tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic
acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
[0039] Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are polycarboxylate builders of particular importance for heavy duty liquid
detergent formulations due to their availability from renewable resources and their
biodegradability. Citrates can also be used in granular compositions, especially in
combination with zeolite and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
[0040] Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates
and the related compounds disclosed in U.S Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the C
5-C
20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound
of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsucccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred)
and 2-pentadecenylsuccinate. Laurylsuccinates are the preferred builders of this group,
and are described in European Patent Application 0,200,263, published November 5,
1986.
[0041] Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield
et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7,
1967. See also Diehl U.S. Patent 3,723,322
[0042] Fatty acids, e.g., C
12-C
18 monocarboxylic acids, can also be incorporated into the compositions alone, or in
combination with the aforesaid builders, especially citrate and/or the succinate builders,
to provide additional builder activity. Such use of fatty acids will generally result
in a diminution of sudsing, which should be taken into account by the formulator.
[0043] In situations where phosphorus-based builders can be used, and especially in the
formulation of bars used for hand-laundering operations, the various alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate
and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021; 3,400,148 and 3,422,137) can also be used.
[0044] Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric
laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based
stains, for example, and for the prevention of refugee dye transfer, and for fabric
restoration. The enzymes to be incorporated include proteases, amylases, lipases,
cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may
also be included. They may be of any suitable origin, such as vegetable, animal, bacterial,
fungal and yeast origin. However, their choice is governed by several factors such
as pH-activity and/or stability optima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes are preferred, such
as bacterial amylases and proteases. and fungal cellulases.
[0045] Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by weight,
more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated
otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably
0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually
present in such commercial preparations at levels sufficient to provide from 0.005
to 0.1 Anson units (AU) of activity per gram of composition.
[0046] Suitable examples of proteases are the subtilisins which are obtained from particular
strains of B. subtilis and B. licheniforms. Another suitable protease is obtained
from a strain of Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold by Novo Industries A/S under the registered trade name ESPERASE.
The preparation of this enzyme and analogous enzymes is described in British Patent
Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based
stains that are commercially available include those sold under the tradenames ALCALASE
and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics,
Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application
130,756, published January 9, 1985) and Protease B (see European Patent Application
0251446, published January 7, 1988, and European Patent Application 130,756, Bott
et al, published January 9, 1985). Most preferred is what is called herein "Protease
C", which is a variant of an alkaline serine protease from
Bacillus, particularly
Bacillus lentus, in which arginine replaced lysine at position 27, tyrosine replaced valine at position
104, serine replaced asparagine at position 123, and alanine replaced threonine at
position 274. Protease C is described in EP 0451244; U.S. Patent No. 5,185,250; and
U.S. Patent No. 5,204,015. Also preferred are protease which are described in copending
Application U.S. Serial No. 08/136,797, entitled "Protease-Containing Cleaning Compositions"
and copending Application U.S. Serial No. 08/136,626, entitled "Bleaching Compositions
Comprising Protease Enzymes". Genetically modified variants, particularly of Protease
C, are also included herein.
[0047] Amylases include, for example, α-amylases described in British Patent Specification
No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo
Industries.
[0048] The cellulase usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which
discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800
or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase
extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME (Novo) is especially useful.
[0049] Suitable lipase enzymes for detergent usage include those produced by microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in
British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487,
laid open to public inspection on February 24, 1978. This lipase is available from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES,
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB
3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter
viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands,
and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa
and commercially available from Novo (see also EPO 341,947) is a preferred lipase
for use herein.
[0050] Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching,"
i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations
to other substrates in the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such
as chloro- and bromo-peroxidase Peroxidase-containing detergent compositions are disclosed,
for example, in PCT International Application WO 89/099813, published October 19,
1989, by O. Kirk, assigned to Novo Industries A/S.
[0051] A wide range of enzyme materials and means for their incorporation into synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January
5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457,
Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March
26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their
incorporation into such formulations, are disclosed in U.S. Patent 4,261,868, Hora
et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various
techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S.
Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application
Publication No. 0 199 405, published October 29, 1986, Venegas. Enzyme stabilization
systems are also described, for example, in U.S. Patent 3,519,570.
[0052] Enzyme Stabilizers - The enzymes employed herein are stabilized by the presence of water-soluble sources
of calcium and/or magnesium ions in the finished compositions which provide such ions
to the enzymes. (Calcium ions are generally somewhat more effective than magnesium
ions and are preferred herein if only one type of cation is being used.) Additional
stability can be provided by the presence of various other art-disclosed stabilizers,
especially borate species: see Severson, U.S. 4,537,706. Typical detergents, especially
liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from
5 to 15, and most preferably from 8 to 12, millimoles of calcium ion per liter of
finished composition. This can vary somewhat, depending on the amount of enzyme present
and its response to the calcium or magnesium ions. The level of calcium or magnesium
ions should be selected so that there is always some minimum level available for the
enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
Any water-soluble calcium or magnesium salt can be used as the source of calcium or
magnesium ions, including, but not limited to, calcium chloride, calcium sulfate,
calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate,
and the corresponding magnesium salts. A small amount of calcium ion, generally from
0.05 to 0.4 millimoles per liter, is often also present in the composition due to
calcium in the enzyme slurry and formula water. In solid detergent compositions the
formulation may include a sufficient quantity of a water-soluble calcium ion source
to provide such amounts in the laundry liquor. In the alternative, natural water hardness
may suffice.
[0053] It is to be understood that the foregoing levels of calcium and/or magnesium ions
are sufficient to provide enzyme stability. More calcium and/or magnesium ions can
be added to the compositions to provide an additional measure of grease removal performance.
Accordingly, as a general proposition the compositions herein will typically comprise
from 0.05% to 2% by weight of a water-soluble source of calcium or magnesium ions,
or both. The amount can vary, of course, with the amount and type of enzyme employed
in the composition.
[0054] The compositions herein may also optionally, but preferably, contain various additional
stabilizers, especially borate-type stabilizers. Typically, such stabilizers will
be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%,
more preferably from 0.75% to 3%, by weight of boric acid or other borate compound
capable of forming boric acid in the composition (calculated on the basis of boric
acid). Boric acid is preferred, although other compounds such as boric oxide, borax
and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium
pentaborate) are suitable. Substituted boric acids (e.g, phenylboronic acid, butane
boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.
[0055] Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching
compositions containing a bleaching agent and one or more bleach activators when formulated
appropriately by those skilled in the art. It is believed that the use of bleaching
compounds with the soil dispersing agents of this invention will generally result
in a diminution of bleaching performance, which should be taken into account by the
formulator. When present, bleaching agents will typically be at levels of from 1%
to 30%, more typically from 5% to 20%, of the detergent composition, especially for
fabric laundering. If present, the amount of bleach activators will typically be from
0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising
the bleaching agent-plus-bleach activator.
[0056] The bleaching agents used herein can be any of the bleaching agents useful for detergent
compositions in textile cleaning, hard surface cleaning, or other cleaning purposes
that are now known or become known. These include oxygen bleaches as well as other
bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate)
can be used herein.
[0057] Another category of bleaching agent that can be used without restriction encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class
of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic
acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued
November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985,
European Patent Application 0,133,354, Banks et al, published February 20, 1985, and
U.S Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching
agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent
4,634,551, issued January 6, 1987 to Burns et al.
[0058] Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds
include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach
(e.g., OXONE, manufactured commercially by DuPont) can also be used.
[0059] A preferred percarbonate bleach comprises dry particles having an average particle
size in the range from 500 micrometers to about 1,000 micrometers, not more than about
10% by weight of said particles being smaller than 200 micrometers and not more than
10% by weight of said particles being larger than 1,250 micrometers. Optionally, the
percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate
is available from various commercial sources such as FMC, Solvay and Tokai Denka.
[0060] Mixtures of bleaching agents can also be used.
[0061] Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably
combined with bleach activators, which lead to the
in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various nonlimiting examples of activators
are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S.
Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also be used. See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
[0062] Highly preferred amido-derived bleach activators are those of the forrnulae:
R
1N(R
5)C(O)R
2C(O)L or R
1C(O)N(R
5)R
2C(O)L
wherein R
1 is an alkyl group containing from about 6 to about 12 carbon atoms, R
2 is an alkylene containing from 1 to about 6 carbon atoms, R
5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms,
and L is any suitable leaving group. A leaving group is any group that is displaced
from the bleach activator as a consequence of the nucleophilic attack on the bleach
activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
[0063] Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate,
and mixtures thereof as described in U.S. Patent 4,634,551.
[0064] Another class of bleach activators comprises the benzoxazin-type activators disclosed
by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990. A highly preferred
activator of the benzoxazin-type is:
[0065] Still another class of preferred bleach activators includes the acyl lactam activators,
especially acyl caprolactans and acyl valerolactams of the formulae:
wherein R
6 is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon
atoms, or a substituted phenyl group containing from 6 to 18 carbons. Highly preferred
lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl
caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,
nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses
acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
[0066] Bleaching agents other than oxygen bleaching agents are also known in the art and
can be utilized herein. One type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al.
If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight,
of such bleaches, especially sulfonate zinc phthalocyanine.
[0067] If desired, the bleaching compounds can be catalyzed by means of a manganese compound.
Such compounds are well known in the an and include, for example, the manganese-based
catalysts disclosed in U.S. Pat. 5.246.621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416;
U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2,
and 544,490A1; Preferred examples of these catalysts include Mn
IV2(u-O)
3(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(PF
6)
2, Mn
III2(u-O)
1(u-OAc)
2 (1,4,7-trimethyl-1,4,7-triazacyclononane)
2-(ClO
4)
2, Mn
IV4(u-O)
6(1,4,7-triancyclono-nane)
4(ClO
4)
4, Mn
IIIMn
IV4(u-O)
1(u-OAc)
2-(1,4,7-trimethyl-1,4,7-triazacyclono-nane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH
3)
3(PF
6)
, and mixtures thereof. Other metal-based bleach catalysts include those disclosed
in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various
complex ligands to enhance bleaching is also reported in the following United States
Patents 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161;
and 5,227,084.
[0068] As a practical matter, and not by way of limitation, the compositions and processes
herein can be adjusted to provide on the order of at least one part per ten million
of the active bleach catalyst species in the aqueous washing medium, and will preferably
provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst
species in the laundry liquor.
[0069] Polymeric Soil Release Agent - In addition to the soil dispersing agents of this invention, any polymeric soil
release agent known to those skilled in the art can optionally be employed in the
compositions and processes of this invention. Polymeric soil release agents are characterized
by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers,
such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic
fibers and remain adhered thereto through completion of washing and rinsing cycles
and, thus, serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to treatment with the soil release agent to be more easily cleaned
in later washing procedures.
[0070] The polymeric soil release agents useful herein especially include those soil release
agents having: (a) one or more nonionic hydrophile components consisting essentially
of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or
(ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of
from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene
unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii)
a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene
units wherein said mixture contains a sufficient amount of oxyethylene units such
that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity
of conventional polyester synthetic fiber surfaces upon deposit of the soil release
agent on such surface, said hydrophile segments preferably comprising at least 25%
oxyethylene units and more preferably, especially for such components having 20 to
30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe
components comprising (i) C
3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C
3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C
4-C
6 alkylene or oxy C
4-C
6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably
polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are
present in the form of C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose
derivatives are amphiphilic, whereby they have a sufficient level of C
1-C
4 alkyl ether and/or C
4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces
and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic
fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and
(b).
[0071] Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization
of from 200, although higher levels can be used, preferably from 3 to 150, more preferably
6 to 100. Suitable oxy C
4-C
6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO
3S(CH
2)
nOCH
2CH
2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
[0072] Polymeric soil release agents useful in the present invention also include cellulosic
derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene
terephthalate or propylene terephthalate with polyethylene oxide or polypropylene
oxide terephthalate, and the like. Such agents are commercially available and include
hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents
for use herein also include those selected from the group consisting of C
1-C
4 alkyl and C
4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol,
et al.
[0073] Soil release agents characterized by poly(vinyl ester) hydrophobe segments include
graft copolymers of poly(vinyl ester), e.g., C
1-C
6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application 0 219 048, published
April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind
include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West
Germany).
[0074] One type of preferred soil release agent is a copolymer having random blocks of ethylene
terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of
this polymeric soil release agent is in the range of from about 25,000 to about 55,000.
See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to
Basadur issued July 8, 1975.
[0075] Another preferred polymeric soil release agent is a polyester with repeat units of
ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units
together with 90-80% by weight of polyoxyethylene terephthalate units, derived from
a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer
include the commercially available material ZELCON 5126 (from Dupont) and MILEASE
T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0076] Another preferred polymeric soil release agent is a sulfonated product of a substantially
linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
These soil release agents are described fully in U.S. Patent 4,968,451, issued November
6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric
compounds of U S Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0077] Preferred polymeric soil release agents also include the soil release agents of U.S.
Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic,
especially sulfoaroyl, end-capped terephthalate esters.
[0078] Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl
units, sulfoisophthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat
units form the backbone of the oligomer and are preferably terminated with modified
isethionate end-caps. A particularly preferred soil release agent of this type comprises
about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy
units in a ratio of from 1.7 to 1.8, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer,
of a crystalline-reducing stabilizer, preferably selected from the group consisting
of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
[0079] If utilized, soil release agents will generally comprise from about 0.01% to 10.0%,
by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably
from 0.2% to 3.0%.
[0080] Chelating Agents - The detergent compositions herein may also optionally contain one or more iron
and/or manganese chelating agents. Such chelating agents can be selected from the
group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures therein, all as hereinafter defined. Without
intending to be bound by theory, it is believed that the benefit of these materials
is due in part to their exceptional ability to remove iron and manganese ions from
washing solutions by formation of soluble chelates.
[0081] Amino carboxylates useful as optional chelating agents include ethylene-diaminetetracetates,
N-hydroxyethylethylenediaminetricetates, nitrilotriacetates, ethylene-diamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriaminepenta-acetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
[0082] Amino phosphonates are also suitable for use as chelating agents in the compositions
of the invention when at lease low levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more
than 6 carbon atoms.
[0083] Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions
herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
[0084] A preferred biodegradable chelator for use herein is ethylenediamine disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November
3, 1987, to Hartman and Perkins.
[0085] If utilized, these chelating agents will generally comprise from 0.1% to 10% by weight
of the detergent compositions herein. More preferably, if utilized, the chelating
agents will comprise from 0 1% to 3 0% by weight of such compositions.
[0086] Clay Soil Removal/Anti-redeposition Agents - In addition to the soil dispersing agents of this invention, the compositions of
the present invention can also optionally contain charged, water-soluble, highly ethoxylated
amines having polar and clay soil removal and antiredeposition properties. Granular
detergent compositions which contain these compounds typically contain from 0.01%
to 10.0% by weight of the charged, highly ethoxylated amines; liquid detergent compositions
typically contain 0.01% to 5%.
[0087] If employed, the most preferred soil release and anti-redeposition agent useful in
this invention is a quaternized ethoxylated tetraethylenepentamine. Exemplary ethoxylated
amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1,
1986. Another group of preferred clay soil removal-antiredeposition agents are the
cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink,
published June 27, 1984. Other clay soil removal/antiredeposition agents which can
be used include the ethoxylated amine polymers disclosed in European Patent Application
111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in
European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine
oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other
charged clay soil removal and/or anti redeposition agents known in the art can also
be utilized in the compositions herein. Another type of preferred antiredeposition
agent includes the carboxy methyl cellulose (CMC) materials. These materials are well
known in the art.
[0088] Polymeric Dispersing Agents - Optionally, additional polymeric dispersing agents can advantageously be utilized
at levels from 0.1% to 7%, by weight, in the compositions herein, especially in the
presence of zeolite and/or layered silicate builders. If employed in the compositions
herein, suitable polymeric dispersing agents include polymeric polycarboxylates and
polyethylene glycols, although others known in the art can also be used. It is believed,
though it is not intended to be limited by theory, that polymeric dispersing agents
enhance overall detergent builder performance, when used in combination with other
builders (including lower molecular weight polycarboxylates) by crystal growth inhibition,
particulate soil release peptization, and anti-redeposition.
[0089] Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric
acids that can be polymerized to form suitable polymeric polycarboxylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic
acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the
polymeric polycarboxylates herein or monomeric segments, containing no carboxylate
radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that
such segments do not constitute more than 40% by weight.
[0090] Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts
of polymerized acrylic acid. The average molecular weight of such polymers in the
acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000
and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and substituted ammonium
salts. Soluble polymers of this type are known materials. Use of polyacrylates of
this type in detergent compositions has been disclosed, for example in Diehl, U.S.
Patent 3,308,067, issued March 7, 1967.
[0091] Acrylic/maleic-based copolymers may also be used as a preferred component of the
dispersing/anti-redeposition agent. Such materials include the water-soluble salts
of copolymers of acrylic acid and maleic acid. The average molecular weight of such
copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably
from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate
to maleate segments in such copolymers will generally range from 30:1 to 1:1, more
preferably from 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid
copolymers can include, for example, the alkali metal, ammonium and substituted ammonium
salts. Soluble acrytate/maleate copolymers of this type are known materials which
are described in European Patent Application No. 66915, published December 15, 1982,
as well as in EP 193,360, published September 3, 1986, which also describes such polymers
comprising hydroxypropylacrylate. Still other useful dispersing agents include the
maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP
193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
[0092] Another polymeric material which can be included is polyethylene glycol (PEG). PEG
can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition
agent. Typical molecular weight ranges for these purposes range from about 500 to
100,000, preferably from 1,000 to 50,000, more preferably from about 1,500 to 10,000.
[0093] Polyaspartate and polyglutamate dispersing agents may also be used, especially in
conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably
have a molecular weight (avg.) of 10,000
[0094] Brightener - Any optical brighteners or other brightening or whitening agents known in the art
can be incorporated at levels typically from 0.05% to 1.2%, by weight, into the detergent
compositions herein. Commercial optical brighteners which may be useful in the present
invention can be classified into subgroups, which include, but are not necessarily
limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other
miscellaneous agents. Examples of such brighteners are disclosed in "The Production
and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John
Wiley & Sons, New York (1982).
[0095] Specific examples of optical brighteners which are useful in the present compositions
are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988.
These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available
from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil-
benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;
1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-strylnapth-[1,2-d]oxazole;
and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Patent 3,646,015,
issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
[0096] Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated
into the compositions of the present invention. Suds suppression can be of particular
importance in the so-called "high concentration cleaning process" as described in
U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
[0097] A wide variety of materials may be used as suds suppressors, and suds suppressors
are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia
of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons,
Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic
fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September
27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used
as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably
12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
[0098] The detergent compositions herein may also contain non-surfactant suds suppressors.
These include, for example: high molecular weight hydrocarbons such as paraffin, fatty
acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic C
18-C
40 ketones (e.g., stearone). Other suds inhibitors include N-akylated amino triazines
such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed
as products of cyanuric chloride with two or three moles of a primary or secondary
amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates
such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.,
K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin
and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid
at room temperature and atmospheric pressure, and will have a pour point in the range
of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure).
It is also known to utilize waxy hydrocarbons, preferably having a melting point below
100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent
compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having
from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion,
is intended to include mixtures of true paraffins and cyclic hydrocarbons.
[0099] Another preferred category of non-surfactant suds suppressors comprises silicone
suds suppressors. This category includes the use of polyorganosiloxane oils, such
as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins,
and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane
is chemisorbed or fused onto the silica. Silicone suds suppressors are well known
in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5,
1981 to Gandolfo et al and European Patent Application 0 354 016 published February
7, 1990, by Starch, M. S.
[0100] Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates
to compositions and processes for defoaming aqueous solutions by incorporating therein
small amounts of polydimethylsiloxane fluids.
[0101] Mixtures of silicone and silanated silica are described, for instance, in German
Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in
granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta
et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
[0102] An exemplary silicone based suds suppressor for use herein is a suds suppressing
amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1,500 cs. at 25°C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed
of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 Sio1/2 units and to SiO2 units of from 0.6:1 to 1.2:1; and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
[0103] In the preferred silicone suds suppressor used herein, the solvent for a continuous
phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol
copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone
suds suppressor is branched/crosslinked and preferably not linear.
[0104] To illustrate this point further, typical liquid laundry detergent compositions with
controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to
0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor,
which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture
of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing
silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote
the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least
one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene
glycol having a solubility in water at room temperature of more than about 2 weight
%; and without polypropylene glycol. Similar amounts can be used in granular compositions,
gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February
22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line
46 through column 4, line 35.
[0105] The silicone suds suppressor herein preferably comprises polyethylene glycol and
a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular
weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol
and polyethylene/polypropylene copolymers herein have a solubility in water at room
temperature of more than 2 weight %, preferably more than 5 weight %.
[0106] The preferred solvent herein is polyethylene glycol having an average molecular weight
of less than 1,000, more preferably between 100 and 800, most preferably between 200
and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG
200/PEG 300. Preferred is a weight ratio of between 1:1 and 1:10, most preferably
between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene
glycol.
[0107] The preferred silicone suds suppressors used herein do not contain polypropylene
glycol, particularly of 4,000 molecular weight. They also preferably do not contain
block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
[0108] Other suds suppressors useful herein comprise the secondary alcohols (e.g.. 2-alkyl
alkanols) and mixtures of such alcohols with silicone oils, such as the silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include
the C
6-C
16 alkyl alcohols having a C
1-C
16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under
the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark
ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol
- silicone at a weight ratio of 1:5 to 5:1.
[0109] For any detergent compositions to be used in automatic laundry washing machines,
suds should not form to the extent that they overflow the washing machine. Suds suppressors,
when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing
amount" is meant that the formulator of the composition can select an amount of this
suds controlling agent that will sufficiently control the suds to result in a low-sudsing
laundry detergent for use in automatic laundry washing machines.
[0110] The compositions herein will generally comprise from 0% to 5% of suds suppressor.
When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein,
will be present typically in amounts up to 5%, by weight, of the detergent composition.
Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight,
of the detergent composition, although higher amounts may be used. This upper limit
is practical in nature, due primarily to concern with keeping costs minimized and
effectiveness of lower amounts for effectively controlling sudsing. Preferably from
0.01% to 1% of silicone suds suppressor is used, more preferably from 025% to 0.5%.
As used herein, these weight percentage values include any silica that may be utilized
in combination with polyorganosiloxane, as well as any adjunct materials that may
be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts
ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors
are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels
can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight
of the finished compositions.
[0111] Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays
of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as
other softener clays known in the art, can optionally be used typically at levels
of from 0.5% to 10% by weight in the present compositions to provide fabric softener
benefits concurrently with fabric cleaning. Clay softeners can be used in combination
with amine and cationic softeners as disclosed for example, in U.S. Patent 4,375,416,
Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September
22, 1981.
[0112] Dye Transfer Inhibiting Agents - In addition to the soil dispersing agents herein, the compositions of the present
invention may also include one or more materials effective for inhibiting the transfer
of dyes from one fabric to another during the cleaning process. Generally, such dye
transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,
peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01%
to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably
from 0.05% to 2%.
[0113] More specifically, the polyamine N-oxide polymers preferred for use herein contain
units having the following structural formula: R-A
x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the
N-O group can form part of the polymerizable unit or the N-O group can be attached
to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=;
x is 0 or 1, and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or
alicyclic groups or any combination thereof to which the nitrogen of the N-O group
can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine, piperidine and derivatives thereof.
[0114] The N-O group can be represented by the following general structures:
wherein R
1, R
2, R
3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof;
x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part
of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides
has a pKa <10, preferably pKa <7, more preferred pKa <6.
[0115] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof. These polymers include random or block copolymers where one
monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine
N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide polymer can
be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
The polyamine oxides can be obtained in almost any degree of polymerization. Typically,
the average molecular weight is within the range of 500 to 1,000,000; more preferred
1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials
can be referred to as "PVNO".
[0116] The most preferred polyamine N-oxide useful in the detergent compositions herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000
and an amine to amine N-oxide ratio of 1:4.
[0117] Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a
class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average
molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light scattering as described in Barth, et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which
are incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably
from 0.8:1 to 0.3:1, most preferably from 06:1 to 0.4:1. These copolymers can be either
linear or branched.
[0118] The present invention compositions also may employ a polyvinylpyrrolidone ("PVP")
having an average molecular weight of from 5,000 to 400,000, preferably from 5,000
to 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled
in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated
herein by reference. Compositions containing PVP can also contain polyethylene glycol
("PEG") having an average molecular weight from about 500 to about 100,000, preferably
from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered
in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
[0119] The detergent compositions herein may also optionally contain from 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners which also provide a dye
transfer inhibition action. If used, the compositions herein will preferably comprise
from 0.01% to 1% by weight of such optical brighteners.
[0120] The hydrophilic optical brighteners useful in the present invention are those having
the structural formula:
wherein R
1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R
2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
[0121] When in the above formula, R
1 is anilino, R
2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic
acid and disodium salt. This particular brightener species is commercially marketed
under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent compositions
herein.
[0122] When in the above formula, R
1 is anilino, R
2 is N-2-hydroxyethyl-N-2-methylamine and M is a cation such as sodium, the brightener
is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
[0123] When in the above formula, R
1 is anilino, R
2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid, sodium salt. This particular brightener species is commercially marketed under
the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
[0124] The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition performance benefits when used
in combination with the selected polymeric dye transfer inhibiting agents hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX
and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous
wash solutions than does either of these two detergent composition components when
used alone. Without being bound by theory, it is believed that such brighteners work
this way because they have high affinity for fabrics in the wash solution and therefore
deposit relatively quickly on these fabrics. The extent to which brighteners deposit
on fabrics in the wash solution can be defined by a parameter called the "exhaustion
coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in the wash
liquor. Brighteners with relatively high exhaustion coefficients are the most suitable
for inhibiting dye transfer in the context of the present invention.
[0125] Of course, it will be appreciated that other, conventional optical brightener types
of compounds can optionally be used in the present compositions to provide conventional
fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such
usage is conventional and well-known to detergent formulations.
[0126] Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included
in the compositions herein, including other active ingredients, carriers, hydrotropes,
processing aids, dyes or pigments, solvents for liquid formulations, solid fillers
for bar compositions, etc. If high sudsing is desired, suds boosters such as the C
10-C
16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
The C
10-C
14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surfactants such as the amine
oxides, betaines and sultaines noted above is also advantageous. If desired, soluble
magnesium salts such as MgCl
2 and MgSO
4, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to
enhance grease removal performance.
[0127] Various detersive ingredients employed in the present compositions optionally can
be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate,
then coating said substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admixed with a surfactant before being absorbed into the porous substrate.
In use, the detersive ingredient is released from the substrate into the aqueous washing
liquor, where it performs its intended detersive function.
[0128] To illustrate this technique in more detail, a porous hydrophobic silica (trademark
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5%
of C
13-15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant
solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring
in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be
used). The resulting silicone oil dispersion is emulsified or otherwise added to the
final detergent matrix. By this means, ingredients such as the aforementioned enzymes,
bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers,
fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents,
including liquid laundry detergent compositions.
[0129] Liquid detergent compositions can contain water and other solvents as carriers. Low
molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol,
and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant,
but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to
6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol)
can also be used. The compositions may contain from 5% to 90%, typically 10% to 50%
of such carriers.
[0130] The detergent compositions herein will preferably be formulated such that, during
use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and
12, preferably between 7.5 and 11. Techniques for controlling pH at recommended usage
levels include the use of buffers, alkalis, acids, etc., and are well known to those
skilled in the art.
EXAMPLE I
[0131] Ethoxylation of poly(ethyleneimine) with average molecular weight of 1.200 - To a 250ml 3-neck round bottom flask equipped with a claisen head, thermometer
connected to a temperature controller (Therm-O-Watch™, I
2R), sparging tube, and mechanical stirrer is added poly(ethyleneimine) MW 1200 (Polysciences,
65.6g, 0.055 mole). Ethylene oxide gas (Liquid Carbonics) is added via the sparging
tube under argon at approximately 140°C with very rapid stirring until a weight gain
of 16.8g (corresponding to 0.25 ethoxy units) is obtained. A 25g portion of this yellow
gel-like material is saved. Ethylene oxide is added to the remaining material as described
above until a weight gain of 11.7g (corresponding to a total of 0.50 ethoxy units)
is obtained. A 25g portion of this yellow gel-like material is saved. Ethylene oxide
is added to the remaining material as described above until a weight gain of 8.3g
(corresponding to a total of 0.78 ethoxy units) is obtained. A 25g portion of this
yellow gel-like material is saved. Ethylene oxide is added to the remaining material
as described above until a weight gain of 3.4g (corresponding to a total of 1 ethoxy
unit) is obtained to afford 27.4g of orange gel-like material.
EXAMPLE II
[0132] Ethoxylation of poly(ethyleneimine) with average molecular weight of 1.800 - To a 250ml 3-neck round bottom flask equipped with a claisen head, thermometer
connected to a temperature controller (Therm-O-Watch™, I
2R), sparging tube, and mechanical stirrer is added poly(ethyleneimine) MW 1800 (Polysciences,
50.0g, 0.028 mole). Ethylene oxide gas (Liquid Carbonics) is added via the sparging
tube under argon at approximately 140°C with very rapid stirring until a weight gain
of 52g (corresponding to 1.2 ethoxy units) is obtained. A 50g portion of this yellow
gel-like material is saved. To the remaining material is added potassium hydroxide
pellets (Baker, 0.30g, 0.0053 mol). after the potassium hydroxide dissolves, ethylene
oxide is added as described above until a weight gain of 60g (corresponding to a total
of 4.2 ethoxy units) is obtained. A 53g portion of this brown viscous liquid is saved.
Ethylene oxide is added to the remaining material as described above until a weight
gain of 35.9g (corresponding to a total of 7.1 ethoxy units) is obtained to afford
94.9g of dark brown liquid. The potassium hydroxide in the latter two samples is neutralized
by adding the theoretical amounts of methanesulfonic acid.
EXAMPLE III
[0133] Benzylation of Poly(ethyleneimine) MW 1800 to 10 Mole% Relative to Nitrogens, and
Its Subsequent Ethoxylation - A 100mL, three neck, round bottom flask is equipped with a magnetic stir bar, a
condenser, a thermometer, a temperature control device (Therm-O-Watch™, I
2R), and an addition funnel. To this reaction flask is added the poly(ethyleneimine)
MW 1800 (Polysciences Inc, 20.0g, 0.011 moles). To the addition funnel is added the
benzyl chloride (Aldrich, 5.9g, 0.047 moles), which is enough to react with 10 mole%
of the available nitrogens in the poly(ethyleneimine). The reaction flask is now heated
to 100°C under argon, and at this temperature the benzyl chloride is dripped in at
a rate of about 1 drop every 3 seconds. An exotherm of approximately 10° C is noted
during the addition procedure. After the addition of benzyl chloride is complete,
the reaction heating is continued at 100°C under argon for 5 hours. After a brief
cooling period, the orange colored product is dissolved in methanol to form a 20%
solution by weight. To this solution is added the theoretical amount of a 25% solution
by weight of sodium methoxide in methanol (Aldrich, 10.1g, .0.047moles) to neutralize
the HCl formed during the reaction. The precipitated salt is removed from the yellow
solution by filtration using aspirator vacuum. The solution is then stripped of methanol
on a rotary evaporator (Büchi) at 50°C and aspirator vacuum to give benzylated PEI-1800.
[0134] Ethoxylation of Benzylated PEI-1800 - A 250mL, three neck, round bottom flask is
equipped with a gas inlet tube with a fitted glass tip, a thermometer, a temperature
control device (Therm-O-Watch™, I
2R), and a motorized stirrer with a glass shaft and Teflon blade. The benzylated poly(ethyleneimine)
(10.2g, 0.005 moles) as prepared above is placed in the reaction flask. The reaction
is taken up to 150°C under argon, with vigorous stirring. At this point, ethylene
oxide (Liquid Carbonics) is bubbled into the reaction vessel until a weight gain of
3.7g is noted in the product (this weight gain corresponds to an E=0.5 level of ethoxylation
relative to the available nitrogen sites on the polymer). A portion of this product
(4.1g) is removed from the reaction vessel, and the reaction temperature is sustained
at 150°C. The flow of ethylene oxide into the reaction is continued until a product
weight gain of 2.7g is achieved (E=1 level of ethoxylation). A portion of the brown
product oil (5.4g) is removed from the reaction, and 1 mole% of potassium hydroxide
is added as a catalyst. The ethylene oxide flow is continued until an additional 13.4g
of weight gain is noted in the product (E=5.6 level of ethoxylation). Again, a portion
of this product (9.5g) is removed and the ethoxylation continued as above after additional
potassium hydroxide catalyst (0.112g) is added . The product gains 12.8g of weight
during this leg of the ethoxylation procedure (E=14). The ethoxylation is discontinued,
and this final product saved. The base catalyst in the last two ethoxylations is neutralized
with methanesulfonic acid (Aldrich). Each of the polymer samples is tested for water
solubility in deionized water in small screw cap vials. The E=5.6 and E=14 samples
are soluble at 10% solution by weight, and the E=1 sample is soluble at 1% solution.
The E=0.5 sample is only partially soluble at 1% solution. A slightly cloudy suspension
is formed in this case.
EXAMPLE IV
[0135] Synthesis of Poly(ethyleneimine) MW1800, Propoxylated to P=1, and then Ethoxylated
to E=6.5 and 10.1 - A 250 mL, three neck, round bottom flask is equipped with a magnetic stir bar,
a dry ice condenser, an addition funnel, a thermometer, and a temperature control
device (Therm-O-Watch™, I
2R). To this reaction flask is added the poly(ethyleneimine) MW 1800 (Polysciences
Inc., 20.2 g, 0.011 moles), and an equal mass of distilled water. To the addition
funnel is added the propylene oxide (Aldrich, 11.8g, 0.203 moles). The reaction flask
is now heated to 80°C under argon, and at this temperature the propylene oxide is
dripped into the reaction in small increments over an hour. The addition of the propylene
oxide causes an exotherm. Therefore, the addition rate is controlled so that the reaction
temperature never goes over about 90°C. After all of the propylene oxide has been
added, the heating of the reaction mixture is continued for another hour until no
further propylene oxide reflux is observed. The product solution is transferred to
a 250 mL round bottom flask, and stripped of water on the rotary evaporator (Büchi)
at 60°C and aspirator vacuum. To part of the viscous, transparent yellow product (35.1g,
0.008 moles) is added 3.8g of a 25% solution of sodium methoxide in methanol (Aldrich).
The flask is then put on the Kugelrohr (Aldrich) at 160°C and 2mm Hg for 5 hours until
all of the methoxide salt is dissolved and the methanol and any residual water distilled
off.
[0136] The above product (17.0g, 0.004 moles) is transferred to a 250 mL, three neck, round
bottom flask equipped with a gas inlet tube with a fritted glass tip, a thermometer,
a temperature control device (Therm-O-Watch™, I
2R), and a motorized stirrer with a glass shaft and Teflon blade. The reaction is taken
up to 150°C under argon, with vigorous stirring. At this point, the reaction vessel
is thoroughly flushed with a heavy stream of argon for approximately 15 minutes. The
ethylene oxide gas (Liquid Carbonics) is then bubbled through the reaction until a
weight gain of 45.0g is noted in the product (this weight gain corresponds to an E=6.5
level of ethoxylation relative to the available nitrogen sites on the polymer). A
portion of the golden colored product (30.2g) is removed from the reaction vessel,
and the reaction temperature is maintained at 150°C. The reaction system is again
purged at this point with a heavy flow of argon for about 15 minutes. The flow of
ethylene oxide is resumed after the purging until a weight gain of 12.5g is recorded
in the product (E=10.1 level of ethoxylation). The product color at this point is
essentially the same as the previous E level. The base catalyst in each ethoxylation
product is neutralized with methanesulfonic acid (Aldrich). Each of the polymer samples
is found to be soluble at 10% solution in deionized water.
EXAMPLE V
[0137] Benzoylation (25 mol%) and Subsequent Ethoxylation of Poly(ethyleneimine), MW 600 - A 250 mL, three neck, round bottom flask is equipped with a magnetic stir bar,
a thermometer, a temperature control device (Therm-O-Watch™, I
2R), a modified Claisen head, and a condenser set for distillation. To this reaction
flask is added the poly(ethyleneimine), MW 600 (Polysciences Inc., 61.9 g, 0.103 moles),
and methyl benzoate (Aldrich, 48.7 g, 0.358 moles). The reaction is heated at 150°C
for 3 hours under argon as methanol distills over. The product is a viscous, bright
yellow oil (of which 10g is saved). About 82.7 g of the product is added to a 500
mL, three neck, round bottom flask equipped with a gas inlet tube with a fitted glass
tip, a thermometer, a temperature control device (Therm-O-Watch™, I
2R), and a motorized stirrer with a glass shaft and Teflon blade. The reaction is taken
up to 150°C under argon, with vigorous stirring. At this point, ethylene oxide (Liquid
Carbonics) is bubbled into the reaction vessel, until a weight gain of 36.0g is achieved
in the product (this weight gain corresponds to about E=1.0 level of ethoxylation
relative to the remaining amino nitrogen NH sites on the polymer). A portion of the
deep red product (19.6g) is removed from the reaction vessel and the reaction temperature
is maintained at 150°C. Potassium hydroxide catalyst (Baker, 0.48 g, 1 mole%) is added
to the reaction and allowed to dissolve. The flow of ethylene oxide is continued into
the reaction until a weight gain of 37.1g is noted (E~2.2 level of ethoxylation).
Again, a portion of this brown product oil (49.2 g) is removed, and the ethoxylation
continued until an additional 66.4g of weight gain is noted in the product (E~5.7).
The ethoxylation is discontinued and this last dark bown product oil is saved. The
base catalyst in the last two ethoxylated products is neutralized with methanesulfonic
acid (Aldrich). The 25 mol% benzoylated PEI-600 forms a hazy white solution in deionized
water at 1%, indicating very limited solubility. The first two ethoxylation products
are fully soluble at 10% solution in deioized water, while the highest E level will
not fully dissolve at this concentration.
EXAMPLE VI
[0138] Synthesis of MW 2018.5, Subsequent Reaction with Poly(ethyleneimine) MW 1800, and
Subsequent Ethoxylation - A 100 mL, three neck, round bottom flask is equipped with a stir bar, a condenser,
an addition funnel, a thermometer, and a temperature control device (Therm-O-Watch™,
I
2R). To this reaction flask is added the poly(ethylene glycol), methyl ether MW 2000
(Aldrich, 60.0g, 0.030 moles). The reaction vessel is taken up to 65°C in order to
melt the poly(ethylene glycol), methyl ether, and then the reaction is cooled to 55°C
and held at this temperature. Thionyl chloride (Aldrich, 11.7g, 0.100 moles) is placed
in the addition funnel, and is dripped into the reaction flask over a 20 minute period.
The reaction is heated overnight under argon at 55°C. The light orange colored waxy
product is taken up in enough methylene chloride (Baker) to form a 30% solution by
weight, and is then stripped on the rotary evaporator at 45°C and aspirator vacuum.
The product pH measures ∼2 at this point with pH strips. The product is dissolved
again in methylene chloride (Baker) at 30% solution and placed in a separatory funnel.
The product solution is washed once with a saturated solution of potassium carbonate
(Baker) in water. The methylene chloride layer is drawn off and stripped again on
the rotary evaporator under the above conditions. The alpha-(2-chloroethyl)-omega-methoxy-poly(oxy-1,2-ethanediyl)
is obtained as an orange, waxy material.
[0139] The alpha-(2-chloroethyl)-omega-methoxy-poly(oxy-1,2-ethanediyl) (13.1g, 0.0065 moles),
the poly(ethyleneimine) MW 1800 (Polysciences, Inc., 11.7 g, 0.0065 moles), and enough
deionized water to make a 35% solution by weight are added to a 100 mL, three neck,
round bottom flask equipped with a stir bar, a condenser, a thermometer, and a temperature
control device (Therm-O-Watch™, I
2R). The clear reaction solution is heated overnight at 80°C under argon. After the
reaction is completed, the theoretical amount of 50% sodium hydroxide solution (Baker)
is added to neutralize the acid formed. The solution is then placed in a 250 mL round
bottom flask and stripped on the rotary evaporator at 60°C and aspirator vacuum. Last
traces of water are removed on a Kugelrohr apparatus (Aldrich) under conditions of
∼2 mmHg and 120°C for 3 hours. A portion of the waxy, yellow product (14.2g, 0.004
moles) is weighed into a 100 mL, three neck, round bottom flask equipped with a gas
inlet tube with a fitted glass tip, a thermometer, a temperature control device (Therm-O-Watch™,
I
2R), and a motorized stirrer with a glass shaft and a Teflon blade. The reaction is
taken up to 150°C under argon, with vigorous stirring. At this point, the ethylene
oxide (Liquid Carbonics) is bubbled into the reaction vessel until a weight gain of
3.4g is noted in the product (this weight gain corresponds to an E=0.7 level of ethoxylation
relative to the available nitrogen sites on the polymer. A portion of this dark yellow
wax is removed, and the flow of ethylene oxide is continued at 150°C until a weight
gain of 2.7g is achieved (E=1.1 level of ethoxylation). Again, a portion of this orange
product is saved, and I mole% potassium hydroxide (Baker) is added as a catalyst.
The ethoxylation is continued at 150° C until a final weight gain of 3.1g is noted
in the product (E=2.0). The base catalyst in this red colored polymer is neutralized
with methanesulfonic acid (Aldrich). All polymer samples show good solubility in deionized
water at 10% solution.
[0140] Example of structure which has degree of ethoxylation = 1 except where MPEG is attached:
EXAMPLE VII
[0141] A granular detergent composition is prepared comprising the following ingredients.
Component |
Weight % |
C13 linear alkyl benzene sulfonate |
22 |
Phosphate (as sodium tripolyphosphate) |
30 |
Sodium carbonate |
14 |
Sodium silicate |
3 |
Zeolite A (0.1-10 microns) |
8.2 |
Nonanoyloxybenzenesulfonate |
3.2 |
Sodium percarbonate* |
4.5 |
Chelant (diethylenetriaminepentaacetic acid) |
0.4 |
Sodium sulfate |
5.5 |
Dispersing agent (Example III) |
0.4 |
Minors, filler** and water |
Balance to 100% |
* Average particle size of 400 to 600 microns. |
**Can be selected from convenient materials such as CaCO3, talc, clay and silicates. |
[0142] In testing the soil dispersing performance of the dispersing agents, the following
test method is used.
[0143] White fabrics, including cotton knit, heavy cotton knit, polycotton, terrycloth,
60/40 polycotton, 50/50 polycotton, and 100% polyester, are used in the testing. Using
a Sears KENMORE washer, the fabrics are desized with a commercial granular detergent
(DASH). The washing is conducted in 0 grains per gallon (gpg) water at a temperature
of 120°F (48.8°C) for 12 minutes, with subsequent rinsing in 0 gpg water at a temperature
of 120°F (48.8°C). This desizing step is done twice and is followed by two additional
wash cycles using only water. The desized fabrics are formed into swatches (5 inches
square being 6.45 cm
2).
[0144] Testing is done in a 5 pot Automatic Mini Washer (AMW) to mimic a hand-wash operation
using standardized conditions. After the AMW pots are filled with 7.6 liters (2 gallons)
of water each, the detergent composition (above) and the dispersing agent are added
to each pot. The clean test swatches are then added alone with an amount of unwashed,
dirty consumer ballast to bring the water/cloth ratio to the desired level of approximately
0.5:1 to about 15 1 (liters:kg). The consumer ballast is split into equal halves between
the dispersing agent containing formula and a pot containing an identical control
formula without dispersing agent. The wash cycle is conducted in 8 grains per gallon
(gpg) water at a temperature of 77°F (25°C) water. The wash cycle consists of a 30
minute soak followed by 10 minute agitation. After the wash cycle, there is a 2 minute
spin cycle, followed by two 2-minute rinse cycles using 8 gpg water at a temperature
of 77°F (25°C). For multicycle testing the test swatches are dried and the above steps
repeated using the same test swatches and new dirty consumer bundles.
[0145] At the end of the last rinse cycle, the test swatches are dried in a dryer Tristimulus
meter readings (L,a,b) are then determined for each test swatch. Whiteness performance
in terms of Hunter Whiteness Values (W) is then calculated according to the following
equation:
[0146] The higher the value for W, the better the whiteness performance. All fabrics display
improved whiteness after laundering compared with fabrics which have not been exposed
to the dispersing agents of this invention.
EXAMPLE VIII
[0147] A laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion
processes and comprises the following:
Component |
Weight % |
C12 linear alkyl benzene sulfonate |
30 |
Phosphate (as sodium tripolyphosphate) |
7 |
Sodium carbonate |
25 |
Sodium pyrophosphate |
7 |
Coconut monoethanolamide |
2 |
Zeolite A (0.1-10 micron) |
5 |
Carboxymethylcellulose |
0.2 |
Polyacrylate (m.w. 1400) |
0.2 |
Dispersing agent (Example I) |
0.5 |
Brightener, perfume |
0.2 |
Protease |
0.3 |
CaSO4 |
1 |
MgSO4 |
1 |
Water |
4 |
Filler* |
Balance to 100% |
*Can be selected from convenient materials such as CaCO3, talc, clay and silicates. |
[0148] In testing the soil dispersing performance of the dispersing agents, the test method
used in Example VII is followed. All fabrics display improved whiteness after laundering
compared with fabrics which have not been exposed to the soil dispersing agents of
this invention.
EXAMPLE IX
[0149] A concentrated liquid detergent composition is prepared comprising the following
ingredients.
Component |
Weight % |
C14-15 alkyl polyethoxylate (2.25) sulfonic acid |
10.6 |
C12-13 linear alkylbenzene sulfonic acid |
12.5 |
C12-13 alkyl polyethoxylate (6.5) |
2.4 |
Sodium cumene sulfonate |
6 |
Ethanol |
1.5 |
1,2 propanediol |
4 |
Monoethanolamine |
1 |
C12-14 fatty acid |
2 |
Dispersing agent (Example II) |
1.5 |
Sodium hydroxide |
to pH 9 or greater |
Minors, filler* and water |
Balance to 100% |
*Can be selected from convenient materials such as CaCO3, talc, clay and silicates. |
[0150] In testing the soil dispersing performance of the dispersing agents, the test method
used in Example VII is followed. All fabrics display improved whiteness after laundering
compared with fabrics which have not been exposed to the soil dispersing agents of
the invention.
[0151] While the compositions and processes of the present invention are particularly useful
in hand-wash fabric laundering operations, it is to be understood that they are also
useful in any cleaning system which involves low water:fabric ratios. One such system
is disclosed in U.S. Patent 4,489,455, Spendel, issued Dec. 25, 1984, which involves
a washing machine apparatus which contacts fabrics with wash water containing detersive
ingredients using a low water: fabric ratio rather than the conventional method of
immersing fabrics in an aqueous bath. Typically, the ratio of water:fabric ranges
from 0.5:1 to 6:1 (liters of water:kg of fabric).
EXAMPLE X
[0152] Using the machine and operating conditions disclosed in U.S. Patent 4,489,455, cited
above, 25 grams of a composition according to Example IX herein are used to launder
fabrics. If desired, sudsing of the composition can be minimized by incorporating
therein from 0.2% to 2% by weight of a fatty acid, secondary alcohol, or silicone
suds controlling ingredient.
Dishwashing Compositions
[0153] Another aspect of the present invention relates to dishwashing compositions, in particular
automatic and manual dishwashing compositions, especially manual liquid dishwashing
compositions.
[0154] Liquid dishwashing compositions according to the present invention preferably comprise
from at least 0.1%, more preferably from 0.5% to 30%, most preferably from 1% to 15%
of the dispersing agent and from 1% to 99.9% of a detersive surfactant.
[0155] Liquid dishwashing compositions according to the present invention may comprise any
of the ingredients listed herein above. In addition the dishwashing compositions may
comprise other ingredients such as bactericides, chelants, suds enhancers, opacifiers
and calcium and magnesium ions.
EXAMPLES XI
[0156] The following liquid compositions of the present invention are prepared by mixing
the listed ingredients in the given amounts.
|
Composition (by weight %) |
Ingredients |
A |
B |
C |
D |
E |
F |
Water |
28.0 |
34.0 |
30.0 |
41.0 |
41.0 |
36.0 |
Ethanol |
13.0 |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
Linear dodecylbenzene |
9.0 |
9.0 |
9.0 |
9.0 |
9.0 |
9.0 |
sulfonic acid |
|
|
|
|
|
|
Sodium cocoyl sulfate |
1.0 |
- |
1.0 |
- |
- |
- |
Condensation product of 1 |
7.0 |
- |
- |
- |
7.0 |
- |
mole of C13-C15 oxoalcohol |
|
|
|
|
|
|
and 7 moles of ethylene oxide |
|
|
|
|
|
|
Condensation product of 1 |
- |
7.0 |
7.0 |
7.0 |
- |
7.0 |
mole of C13-C15 oxoalcohol and |
|
|
|
|
|
|
5 moles of ethylene oxide |
|
|
|
|
|
|
C12-C14 (2hydroxyethyl)dimethyl - |
- |
0.5 |
0.5 |
- |
0.5 |
0.5 |
ammonium chloride |
|
|
|
|
|
|
Dodecenyl succinic acid |
12.5 |
- |
- |
10.0 |
- |
- |
Dodecenyl-tetradecenyl |
- |
- |
- |
- |
10.0 |
- |
succinic acid |
|
|
|
|
|
|
TMS/TDS* |
- |
12.5 |
- |
- |
- |
- |
Sodium tripolyphosphate |
- |
- |
15.0 |
- |
- |
- |
Zeolite |
- |
- |
- |
- |
- |
15.0 |
Citric Acid |
1.0 |
3.0 |
2.8 |
2.8 |
3.0 |
2.8 |
Oleic Acid |
3.0 |
- |
- |
- |
- |
- |
Diethylene triamine penta- |
0.7 |
0.7 |
- |
- |
- |
- |
methylene phosphonic acid |
|
|
|
|
|
|
Hexamethylene diaminetetra |
- |
- |
0.6 |
- |
- |
0.7 |
(methylene phosphonic acid) |
|
|
|
|
|
|
Soil dispersing agent (Ex. 2) |
0.5 |
1.5 |
2.0 |
0.5 |
5.0 |
0.2 |
Protease 8KNPU/g |
0.5 |
- |
- |
- |
- |
- |
Protease 16 KNPU/g |
- |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
Amylase |
0.2 |
- |
- |
- |
- |
0.2 |
Sodium formate |
1.0 |
- |
1.5 |
1.0 |
- |
- |
Sodium acetate |
- |
2.5 |
2.5 |
- |
- |
- |
Magnesium acetate tetrahydrate |
1.7 |
- |
1.7 |
0.1 1 |
- |
- |
Magnesium chloride hexahydrate |
- |
1.7 |
- |
- |
0.1 1 |
0.7 |
Sodium hydroxide |
5.0 |
5.0 |
5.0 |
5.0 |
5.0 |
5.0 |
Perfume and minors |
Balance to 100% |
*(80:20) mixture of tartrate monosuccinate/tartrate disuccinate |
EXAMPLE XII
[0157] An automatic dishwashing composition is as follows.
Ingredient |
%(Wt.) |
Trisodium Citrate |
15 |
Sodium Carbonate |
20 |
Silicate1 |
9 |
Nonionic Surfactant2 |
3 |
Sodium Polyacrylate (m.w. 4000)3 |
5 |
Termamyl Enzyme (60T) |
1.1 |
Savinase Enzyme (12T) |
3.0 |
Soil dispersing Agent (Example I) |
1.0 |
Minors |
Balance to 100%% |
1BRITESIL, PQ Corporation |
2Polyethyleneoxide/polypropyleneoxide low sudser |
3ACCUSOL, Rohm and Haas |
[0158] In the above composition, the surfactant may be replaced by an equivalent amount
of any low-foaming, nonionic surfactant. Example include low-foaming or non-foaming
ethoxylated straight-chain alcohols such as Plurafac™ RA series, supplied by Eurane
Co., Lutensol™ LF series, supplied by BASF Co., Triton™ DF series, supplied by Rohm
& Haas Co., and Synperonic™ LF series, supplied by ICI Co.
[0159] Automatic dishwashing compositions may be in granular, tablet, bar, or rinse aid
form. Methods of making granules, tablets, bars, or rinse aids are known in the art.
See, for instance, applications WO 95/05440, WO 95/12656, WO 95/12653, WO 95/12654,
WO 93/04153, WO 93/21298.
[0160] All of the foregoing granular compositions may be provided as spray-dried granules
or high density (above 600g/l) granules or agglomerates. Such granules (which should
not contain oxidizable components) can comprise, for example, water-soluble silicates
and carbonates.
[0161] While the foregoing examples illustrate the use of the present technology in cleaning/soil
dispersing compositions designed for use in laundering and dishcare, it will be appreciated
by those skilled in the art that the systems herein can be employed under any circumstance
where improved soil dispersing is desired. Thus, the technology of this invention
may be used, for example, to cleanse prosthetic devices such as dentures in dentifrice
compositions and in any other circumstances where soil dispering is advantageous to
the user.